TW506984B - Latent mercaptan stabilizers for improved weatherability of clear halogen-containing polymer compositions and clear halogen-containing polymer compositions containing the same - Google Patents

Abstract

Stabilizer compositions useful for protecting clear polyvinyl chloride and other clear halogen-containing polymer compositions used in the manufacture of exterior weatherable products against discoloration and degradation caused by exposure to ultraviolet light and weathering in addition to heat comprising a latent mercaptan which degrades during processing of the composition at an elevated temperature to liberate a free mercaptan, in combination with a synergistic amount of a free phenyl salicylate compound. The latent mercaptan may be the sole heat stabilizer additive in the stabilizer composition, but the free mercaptan released during processing may also synergize the activity of organic-based or metal-based heat stabilizers such as metal salts and organometallic stabilizers such as organotin carboxylates and organotin mercaptides in the polymer composition. Clear polyvinyl chloride and other clear halogen-containing polymer compositions containing these compounds are also provided which exhibit improved ultraviolet light stability and weatherability without detracting from their thermal performance.

Description

506984 A7 B7 V. Description of the invention (1) Field of the invention The present invention relates to a stabilizer composition which can stabilize the halogen-containing polymer composition against heat, light and weather deterioration. This stabilizer contains a latent thiol (which degrades to a corresponding degradation product when the composition is processed at high temperatures, which contains free thiols), and a very low amount of free phenyl salicylate compounds. The present invention also relates to a halogen-containing polymer composition that is generally susceptible to heat and UV-induced deterioration, which comprises a halogen-containing polymer, a latent thiol degradation product present when the composition is processed at high temperatures ( The product contains a free thiol) and a free phenylsalicylate compound. The present invention also relates to this stabilizer and polymer composition, which additionally contains a very low amount of a metal-based thermal stabilizer, a Lewis acid, an organic-based thermal stabilizer, and a hydrotalche ) Is the thermal stabilizer of the substrate, or other stabilizer synergist. BACKGROUND OF THE INVENTION Various organic polymers are known to undergo physical degradation or color change during polymer processing and when the formed polymer product is exposed to the environment. The main examples of polymers that are susceptible to degradation during processing are halogen-containing polymers, such as ethylene and vinylidene polymers (where halogen is directly bonded to carbon atoms). Poly (vinyl chloride) or PVC, copolymers of vinyl chloride and vinyl acetate, and poly (vinylidene chloride) (the resin used as the main self-adhesive transparent food packaging material) are the most familiar polymers. It must have stability so that it can be manufactured into pipes, window frames, exterior wall panels, bottles, wall coverings, packaging films, etc. When such polymers are processed at high temperatures, undesired color changes often occur most (please read the precautions on the back before filling this page) Order-丨 丨 线 丨-

I I This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) -4-506984 A7 Qi i Discuss i 5. The first 5 to 10 minutes of the invention description (2) and late processing. When a transparent product is required, sometimes the blurring phenomenon that comes with the color change is particularly unpleasant. The addition of ampoules to such polymers is absolutely necessary for the wide use of polymers. In many areas where more effective heat stabilizers have been developed, two categories have emerged: organotinized greed and mixed metal compositions. Organotin-based heat stabilizers are the most effective and have been widely used in rigid PVC. The combined composition of the organotin thiolate compound and the free thiol is a heat stabilizer for rigid PVC which is particularly effective during extrusion. However, it is not completely satisfactory because of several disadvantages of the thiol synergist itself and its inability to be applied to flexible PVC. Many mercaptans emit an unpleasant odor even at room temperature, and the odor becomes worse at the temperature of PVC processing. The oxidative stability of thiols is usually very poor, and the oxidation of free thiols reduces synergy, so a composition with enhanced synergy will be very welcome for the PVC industry. At the same time, many polymer compositions require both biocides and heat stabilizers based on the end use of some polymer-made objects, but organic tin thiolate / thiol combinations are used in such polymers The compounds are usually disappointing because of the ease with which free thiols make biocides (such as the widely used 08-8 (10, 10'-oxybisphene 11 oxarsenic (10, 10'- 〇 ^ 1 ^ $ 〇116] 1〇: ^ 1: 811 ^)) loses its activity. Another disadvantage of this type of thiol-containing thermal stabilizer is that it cannot protect the polymer composition against degradation by ultraviolet light and weather. Function. When exposed to the surrounding light and outdoor climate for a long time, the products formed by these stable polymers will quickly discolor and decompose and lose physical properties. (Please read the precautions on the back before filling this page ) V: _ · ---- t --------- ^ — ------ · ------------------ This paper size is applicable China National Standard (CNS) A4 specification (210 X 297 mm) -5-506984 A7 ______ B7 V. Description of the invention (3) 'such as tensile strength, flexibility, and impact resistance Therefore, the life of the object is shortened. With the increase of the use of halogen-containing polymer compositions for the manufacture of outdoor weather-resistant products (such as vinyl roof panels, window frames, window outlines, wavy roof materials, door strips, etc.) The importance of developing stabilizers that not only protect polymers against the heat encountered during processing and manufacturing, but also protect them against the long-term effects of ambient light and outdoor weathering, has also increased. Transparent products with very poor light stability and weather resistance are particularly needed because they generally do not contain opaque fillers and pigments such as titanium dioxide, which reduce the rate of polymer degradation by inhibiting light penetration.

Ludwig in U.S. Patent No. 3,660,3 31 discloses the use of specific thioethers and thioesters of tetrahydropyran to stabilize vinyl chloride resins. However, there is still a need for better heat stabilizer compositions. What is more needed is a heat stabilizer that can provide a halogen-containing polymer composition (especially a transparent polymer) with improved ultraviolet stability and weather resistance. The thioether / phenyl salicylate stabilizer composition of the present invention can meet this need. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a heat stabilizer composition having a synergistic effect of thiol plus improved ultraviolet stability and weather resistance. Another object of the present invention is to provide a heat stabilizer composition having a synergistic effect of thiol plus improved oxidation stability. It is a further object of the present invention to provide a heat stabilizer composition which is substantially free of the unpleasant odor generally associated with mercaptans. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) -6-(Please read the precautions on the back before filling this page) Order --------- line, ·- ----------------- 506984 A7 B7 V. Description of the invention (4) Another object of the present invention is to provide a thiol with improved biocide compatibility. Synergistic heat stabilizer composition. Furthermore, another object of the present invention is to provide a heat stabilizer composition comprising a latent thiol-containing heat stabilizer and a synergistic dose of a free phenylsalicylic acid compound. Another related object of the present invention is to provide a halogen-containing polymer composition containing clear water and an object substantially transparent to heat, light, and weather stability made of the same, and by latently containing A thiol thermal stabilizer is prepared by combining a free amount of a free phenylsalicylate compound. The above and other objects of the present invention will be made clearer by the following description, and it is achieved by a stabilizer composition which can stabilize the halogen-containing polymer composition against heat, light, and weather deterioration. It consists of mixing a blocked thiol (degraded to release free thiols when processed at high temperatures) and a synergistic dose of a relatively inexpensive free phenyl salicylate compound, of which I believe when the composition When the substance is exposed to ambient light for a long time, the free phenylsalicylate compound undergoes photo-induced Fnes rearrangement and releases a benzophenone compound having a relatively high ultraviolet absorption activity. The above and other objects of the present invention can also be achieved by mixing a clear polymer composition containing a halogen-containing polymer that is generally susceptible to heat and UV-induced deterioration, a protected thiol, and a synergistic dose. Free phenyl salicylate compound), and processing the composition at high temperature, and the latent thiol will be degraded to release the free thiol. , 'Latent thiol', and 'blocked thiol' are used interchangeably throughout this article. The latent thiol can be used alone as a heat stabilizer, or it can be used in conjunction with other paper sizes in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 public love) (Please read the precautions on the back before filling in this Page) I · n I ϋ ϋ βι · ϋ): OJ · * ^ 1 -ϋ ϋ I ^ 1 I n I ^ 1 -H ϋ · ϋ flu w— —wn βτΊ ί an nn ϋ I n I n 1_ϋ i I-. Slim and thin ^ iro Yue Hui discussion 4¾ member r. Xiao f ΛChatu 卞 506984 A7 B7 V. Description of the invention (5) His heat stabilizer is used in combination, for example, a very low amount of organic matter is used as the substrate. Thermal stabilizers, metal-based thermal stabilizers, or Lewis acid. Other degradation products of protected thiols are believed to contain protecting groups. Carbocations, which can be stabilized by molecular structures that share the electron-deficient nature of several groups. Resonance stabilization and neighboring group stabilization are two possible mechanisms for stabilizing carbocations. Carbocations act as intermediates in the early thermal processing of halogen-containing polymers to form stable compounds. Although this mechanism and the formed carbocations are believed to be an inducement for the release of active free thiols, the present invention is not limited to the above-mentioned part for explaining the technique of the present invention. Those skilled in the art will understand the resonance stabilization of nearby protected thiol structures and the stabilization of adjacent groups. Other mechanisms may also occur in other structures shown in the structural formula. Protected thiols (those that can also release active free thiols under thermal and / or chemical degradation conditions when processing polymer compositions containing such protected thiols). In addition, when exposed to ambient light for a long period of time, the photo-induced Fnes rearrangement of the substantial part of phenylsalicylate into its corresponding benzophenone structure is a possible mechanism, from which The stabilizer composition has very high ultraviolet absorption activity. Although this mechanism and the resulting products are believed to be responsible for the production of highly active UV-absorbing compounds, those familiar with the art will appreciate that other mechanisms may also occur to enhance the UV-absorbing stability provided by such compositions and Weatherability. Therefore, the present invention is by no means limited to the aforementioned part which attempts to explain the technology of the present invention. This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) -8- (Please read the precautions on the back before filling this page) ·· ____ Order --------- line 丨------_-- A ---- 506984 A7 Γ-- _ B7 V. Description of the invention (6) Detailed description of the invention The polymer composition of the present invention contains heat and light induced by the auto-oxidation reaction which is usually easy to produce Aggravating polymers such as the halogen-containing polymers described above. The term "halogen-containing polymer" as used herein refers to a halogen-containing polymer or resin in which a halogen is directly bonded to a carbon atom. Of particular interest in the present invention are clear halogen-containing polymer compositions, especially commercially important transparent polyvinyl chloride compositions. In this context, “、” means that the halogen-containing polymer will form a substantially transparent object. Those skilled in the art will understand that such compositions are essentially free of opaque pigments and extenders. The stabilizer composition of the present invention is particularly suitable for providing excellent stability against the deterioration of heat, ultraviolet rays, and weather compared with stabilizer compositions conventionally known in the prior art. I was quite surprised to find that a clear halogen-containing polymer composition specifically designed for outdoor use can be effectively stabilized against light and climate and heat by incorporating a stable effective amount of a stabilizer composition Degradation, wherein the stabilizer composition comprises A) at least one latent thiol, and B) at least one free phenylsalicylate compound. However, after the corresponding opaque dyed or filled halogen-containing polymer composition was stabilized ', no ultraviolet stability and weather resistance benefits were observed. The halogen-containing organic polymer which can be stabilized by the method of the present invention comprises chlorinated polyethylene with 14 to 75% by weight (for example, 27% by weight) of chlorine, chlorinated natural or synthetic rubber, rubber hydrochloride, chlorinated Copolymer of polystyrene, chlorinated polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, vinyl chloride and 1 to 90% (preferably 1 to 30%) copolymerizable ethylene-based unsaturated substances' The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -9- (Please read the precautions on the back before filling this page) i · -------- Order innn 11 n la I l __ 齐 ψ I 丨 才 ί 506984 A7 _____B7__ V. Description of the invention (7) The copolymerizable ethylenically unsaturated material such as vinyl acetate, vinyl butyrate, vinyl benzoate, vinylidene chloride, Diethyl fumarate, diethyl maleate, other alkyl fumarate and alkyl maleate, vinyl propionate, methyl acrylate, 2-ethyl acrylate Hexyl vinegar, butyl propionate and other malonate, methyl propionate; (: methyl hexanoate, ethyl methacrylate, Butyl acrylate and other methacrylic esters, α-chloroacrylate, styrene, trichloroethylene, vinyl ethers such as vinyl ethyl ether, vinyl chloroethyl ether and vinyl phenyl ether, Ethyl ketones such as ethenyl methyl ether and ethynyl phenylene, 1-fluoro-2-chloroethane, propionitrile, chloroacrylonitrile, allyl diacetate, and chloroallyl Diacetate. Common copolymers include vinyl chloride-vinyl acetate (96: 4, sold under the trade name VYNW), vinyl chloride-vinyl acetate (87:13), vinyl chloride-vinyl acetate_maleic acid Acid anhydride (86: 13: 1), vinyl chloride-vinylidene chloride (95: 5), vinyl chloride-diethyl fumarate (95: 5), and vinyl chloride-ethyl 2-ethylhexyl acrylate (80:20). More preferably, the halogen-containing organic polymer is a vinyl halide polymer, more preferably a vinyl chloride polymer. Generally, the vinyl chloride polymer is a monomer consisting of vinyl chloride alone or containing Made from a monomer mixture of at least about 70% by weight of vinyl chloride (based on the total weight of the monomers). Herein, polyvinyl chloride or PVC composition means a polymer containing vinyl halide A rigid PVC composition is a plasticizer-free PVC composition. A semi-rigid PVC composition is one containing about 1 to about 25 parts by weight of a plasticizer per 100 parts by weight of a halogen-containing ethylene polymer. The flexible PVC composition contains about 25 to about 100 parts by weight of a plasticizer per 100 parts by weight of a halogen-containing ethylene polymer. A representative example of the plasticizer is an alkyl ester of a carboxylic acid, and its (please read first Note on the back, fill in this page again) ~ · n > 1 n ϋ nnn a δ, · nnnnn I n I n 1 ^ I- 1- ϋ 1 I il ί 1 J1 n -ϋ n 1 · n ϋ n 1 nn The size of this paper is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) -10- 506984 A7 B7 V. Description of the invention (8) It has 1 to 3 alkyl groups containing 8 to 12 carbon atoms. The alkyl group may be n-octyl, 2-ethylhexyl, nonyl, decyl or dodecyl. Suitable esters include phthalates, benzene-1,2,4-tricarboxylic esters, benzoates, adipates, glutarates, and sebacates. The plasticizer may also be pentaerythritol or an ester thereof. Polymer plasticizers can also be used. The stabilizer composition of the present invention is effective for both flexible and rigid and semi-rigid PVC compositions. In the stabilizer composition of the present invention, the amount of latent thiol and free phenylsalicylate is determined by several factors, including (but not limited to) the specific compound used, the specific resin to be stabilized, and the resin composition. The severity of the heat, light, and climate encountered, and the desired level of stability. Therefore, the amount of each component can be widely varied, and only the stabilizer composition is required to contain sufficient amounts of each component to stabilize the halogenated polymer to resist heat, light, and weather deterioration, and the requirement for free phenyl salicylate Dosage is synergistic to the stabilizer. The stabilizer composition of the present invention usually contains A) about 50 wt% to about 98.8 wt% (preferably about 80 wt% to about 96 wt%) a latent thiol or a mixture of latent thiols (as A) and B ) Based on the total weight), and B) about 1.2 wt% to about 50 wt% (preferably about 4 wt% to about 20 wt%) free phenylsalicylic acid compound or phenylsalicylic acid compound (based on The total weight of A) and B) is the basis). Other compounds that can be included in the stabilizer composition are calculated based on the weight of the halogen-containing polymer. The protected thiols suitable for the present invention are shown in the following formula 1: The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -11-(Please read the precautions on the back before filling in this Page) · nnnnn ϋ ϋ ^ OJ · n I nnnn 1 «I n ϋ nnnn ϋ n. 506984 A7 -------- B7 V. Description of the invention (9 (R7)«-X- (R6), R4 [V] ti3 ″ a where a is 0 or 1 ′ m and η is 0 or 1; y = 1 to 4; when y = 1, z is 1 to 4; and when y is greater than 丨, z is 1; R1 is an alkyl group, an alkylene group, a cycloalkyl group, a cycloalkylene group, an aryl group, an alkaryl group, an aralkyl group, an arylene group, a hydroxyalkyl group, a dihydroxyalkyl group, Hydroxy (polyalkoxy) alkyl, alkoxyalkyl, hydroxyalkoxyalkyl, alkoxy (hydroxyalkyl), alkoxy (fluorenylalkyl), alkoxy (polyalkoxy) alkane Base, oxo (polyalkoxy) carbonylalkyl, carboxyalkyl, alkoxyalkyl, alkoxy (hydroxyalkyl), alkoxyalkoxyalkyl, alkoxy (polyalkoxy) alkane Radical, benzyloxy (polyalkoxy) alkyl, alkylene di (fluorene radical), oxygen radical, radical Shenyuan Group, Jingyuan Oxygen Group, Jingyuan (Polyalkoxy) carbonyl alkyl group, fluorenyl group, fluorenyl group, fluorenyloxycarbonyl alkyl group, Shuyuan Oxygen Group, Yuanyuan Group醯 Amine group) 丨 Endyl group, "Complete oxo group (Polyendoxyl) carbonyl group, Tetrahydropyranyloxy (polyalkoxy) carbonyl group, Tetrahydropyranyloxyalkyl group, Hydroxy aromatic R2, R3, R4, R5, R6, and R7 are hydrogen, hydroxy, fluorenyl, fluorenyl, alkyl, alkylene, aryl, having 1 to 22 carbon atoms, respectively , Haloaryl, alkaryl, aralkyl, hydroxyalkyl, fluorenyl, hydroxyaryl, alkoxyaryl, alkoxyhydroxyaryl, fluorenyl; x is aryl, haloaryl, alkyl Aryl, hydroxyaryl, dihydroxyaryl, alkoxyaryl, arylcycloalkyl, or heteroatom 'or when a is 丨 and ㈤ is 1, r6 and R7 (Please read the notes on the back before filling (This page) ·· ----- Order --------- I. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -12- 506984 A7 ----- B7_____ V. Description of the invention (1〇) Formation of heterocyclic group containing X as attachment point (X is nitrogen A), or when a is 1 and m is 0, one of R1, R3, and R5 together with R7 and X forms a heterocyclic group containing @atomic X (X is selected from oxygen and sulfur); The condition is that when X is a square radical, R6 and R7 are meridian, a is 1 and m is 1, then z is 1 or 2 'and another prerequisite is when R6 #hydroxy or fluorenyl, z is 1. Thiols that can be converted into latent thiols suitable for the purpose of the present invention are known compounds and include alkyl mercaptans, fluorenyl esters, fluorenyl alcohols and fluorenyl carboxylic acids. See USP 3,503,924 and 3,507,827. Alkyl mercaptans having 1 to about 200 carbon atoms and 1 to 4 fluorenyl groups are suitable and include, but are not limited to, the following compounds containing the S-R1 group: (Please read the note on the back first Please fill in this page again) HS-CH- (CH) Rn R19 (MCI) SHI (CH) i-/ ▲ 丨 2, 丨 R14 (MC2) HS-CH- (CH) II R11 R11

5_ (CH); -CH—SH (MC3)

Rl

Rl (MC4)

(CH) i H

I I R1 R11 R11 This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) -13- Α7

〇 〇 I 1 (MC6)

Ru i 丨 1 R11 ^ R19 may be the same or different II y 〇 〇 〇 C-R17, _C_〇_r17, · 〇Η, _sh square base, Cl-Cl8 courtyard or-Η

RU: ^ -H, aryl or C ^ Cu alkyl; R12 is cycloalkyl, cycloalkyl or phenyl; 〇〇II .. II R13 is 〇-C-r17, c-0-R1 ', -SH, aryl or -Η;, its prerequisite is that in formula (MC2), when R12 is phenyl and R13 is -〇Η and! = 〇, -SH group is located on a non-adjacent carbon atom; R14 is -H or a divalent group, and it may contain halogen, hydroxyl, thiol or alkyl -.17

C 〖-Ci8 Yuanji, -〇H ---- Γ ----------- AW -------- Order --------- line l®- ( Please read the notes on the back before filling in this page), ¾ ^ | > L tr t σι ί substituents and when R12 is phenyl, it forms a naphthalene ring with phenyl; 0 〇II II, _〇 一 c -CH = CH-0-0

R

〇 II

〇II 5 is -〇-Q-R18_Q 一 〇—— 〇〇II 1fi II -ο-c-o-R18-0-C-; R16 is -CH3, -CH2CH3, or 〇-〇-C 一 (C , H) i—CH-SH- 丨-

R 11 R17 is -H, or alkyl, alkenyl, aryl, aralkyl Chinese National Standard (CNS) A4 specification (210 X 297 public ^ or aryl group, ring group 506984 A7 — ___ B7 V. Invention Note (12), cycloalkyl; R18 is aryl, Ct-CM alkyl, —CH— (CH) j— (S) f— (CH) i—CH— (Please read the note on the back first Please fill in this page again) R11 R11 R11 i11 or _ (CH2—CH2—〇) b—CH2-CH Bu where b is an integer from 1 to 6; i = 0 or an integer from 1 to 6 (including 6); J = 0, 1, 2, or 3; and f = 1 or 2. The thiol-containing organic compound that is more suitable for the preparation of the latent thiol intermediate of the present invention is a compound represented by formula (MCI), where the rule is- ^, R19 is -H, R1Q is OH or 0-0-C-R17, and 1 = 1; the compound represented by formula (MC2) where R12 is phenyl, rh is -η, R13 is, R14 is -H , 1 = 1 and j = 1; the compound represented by formula (MC3) is 0.

, M II II compounds, wherein Ril is · Η, R15 is -〇-C-CH = CH-c-101 and 1 = 1; a compound represented by formula (MC4), wherein R11 is & i = 1 A compound represented by the formula (MC5), wherein R16 is -C2H5 or 〇¾ 齐 Jfo 曰 慧 讨 infrwrr. 肖 f 乂 η 乂 i towel double-CH2-〇-c- (CH) 丨 -ch-SH R11 R11 R11 is -H and 1 = 1; and a compound represented by formula (MC6), wherein R11 is -H and 1 2-1. Examples of thiol-containing organic compounds represented by the formula (MC 1) include the following compounds (but not limited to this): This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -15- 506984 A7 _ ____ Β7_ V. Description of the invention (13) .hsc12h25 ο hsch2 coc2h5 〇 »hsch2 coc8h17 〇

I HSCHCOC3H17

I ch3 〇 i hsch2 chocc8h17

I ch3 0

II hschcoc12h25 0

I HSCH2 COClgH37 〇 i HSCH2CH2COCgHl7 This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) -16- (Please read the precautions on the back before filling this page)

-0 nnnnnnn „I ° J · nnn in nnn I n ί ϋ ϋ in ϋ Hi-Hi ϋ n ϋ ϋ» in nnn -n ϋ nn II 506984 A7 B7 5. Description of the invention (14) 〇 HSCH2CH2COCuH23 0 HSCH2CH2OCC17H35 ο HSCH2CH2OCCl7 hsch2ch2ch2 occ8h17 〇hsch2 chocch3 0 HSCH2CH2OCCuH23

0II HSCHCOCH3 I This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) -17- (Please read the precautions on the back before filling this page) Order --------- line 丨------ 506984 A7 B7 Man Qi Zou. &Amp; Said Huicai inRSV-l Xiao f 乂 η Zhutu, V. Description of the invention C〇H 0II-hsch, ch2coh 〇i HSCHCOH I ^ ΑοΗη This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -18- (Please read the precautions on the back before filling this page). ·

^^ em · quantity nnn ϋ m ϋ nn ϋ n «^ ϋ · ϋ nmnn I 1 --- n an 1 ^ 1 ϋ n I 506984 A7 B7 V. Description of the invention (16) Formula (MC2) Examples of thiol-containing organic compounds include, but are not limited to, the following compounds:

Examples of the thiol-containing organic compound represented by the formula (MC3) include the following compounds (but not limited thereto): 〇〇1 II hsch2 coch2ch2occh2sh ο 2 > YC〇ch2ch2sh ^^ xoch2ch2sh 〇 (Please read the notes on the back first (Fill in this page again) ·· —— * Line 丨 * Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs II II HSCH2CH2OC (CH2) 4coch2ch2sh 0 0 «, II hsch9ch7occh == chcoch7ch, sh

Q o HSCH2CH2OCCH2CH2COCH2CH2SH Examples of organic compounds containing 'thiols shown by formula (MC4) are (but not limited to the paper size applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) -19-506984 A7 B7 5 、 Invention note 〇7 Here): 〇HSCH2CH2OCCHr OH 〇 J: c-〇ch2ch2sh An example of a thiol-containing organic compound represented by formula (MC5) is (but not limited to): 0 "CH3CH2C (CH2 OCCH2SH) 3 Examples of thiol-containing organic compounds represented by formula (MC6) are (but not limited to): (Please read the precautions on the back before filling this page). · ____ ί 0 0

0 II HSCH2CH2COCH (CH2 OCCH2CH2SH) 2 ο ο

I I HSCH2COCH (CH2OCCH2SH) 2 A thiol compound represented by the formula (MCI) and (MC4) is particularly suitable. One of the advantages of the present invention is that the mercaptan is shielded by a protective group. Therefore, the paper size produced is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 g) -20- Printed by the cooperative 506984 A7 B7 V. Description of the invention (18) The latent thiol can be put into the PVC composition or the like with little or no intrusive odor invading the operator (the operator knows Free thiols will be released as degradation products when the processed composition is heated during general processing (such as extrusion)). The protected compound is more suitable to provide a stable carbocation (having a molecular structure in which the electrons are deficient by the equal sharing of several groups). The resonance stabilization and the stabilization of adjacent groups are two possible stable carbocations. Mechanisms. The more suitable polarized unsaturated compounds are, for example, 3,4-dihydro% an, 2-methoxy-3,4-dihydropyran, styrene, α-methylstyrene, vinylbenzyl chloride, Indene, 2-vinylpyridine, N-vinylpyrrolidone, vinyl acetate, octadecyl vinyl ether, cyclohexyl diethyl ether, ethylene glycol monovinyl ether, allylphenyl ether, trans -Cinnamaldehyde, N-methyl-N-vinylacetamide, N-vinylcaprolactam, isoeugenol and 2-propenylphenol. Compounds having labile halogen atoms and leaving in the form of hydrogen chloride in a condensation reaction with a thiol, such as trityl chloride, benzyl chloride, and bis (chloromethyl) benzene are also suitable . Thiols can also be protected by a condensation reaction with an aldehyde (such as butyraldehyde) or a benzyl alcohol (such as benzyl alcohol). The preferred protective agent is 2-hydroxybenzyl alcohol, an intermediate well known in the perfume, agricultural and plastic industries. Particularly suitable polarized unsaturated compounds are the aforementioned 3,4-dihydropyrans and their derivatives, such as 3,4-dihydro-2-methoxy-2H-pyran, 3,4-di Hydrogen-2-ethoxy-2H-pyran, 3,4-dihydro-2-phenoxy-2H-pyran, 3,4-dihydro-2-methylfluorenyl-2H-pyran, 3 , 4-Dihydro-2-phenoxy-2H-pyran and its homologues such as 2,3-dihydrofuran and its derivatives. 3,4-Dihydro-2-methylfluorenyl-2H-pyran is a Diels-Alder dimerization reaction of acrolein under high temperature and pressure. This paper is in accordance with China National Standard (CNS) A4 (210 X 297). Mm) -21-(Please read the notes on the back before filling this page) · -------- Order ------ 丨! line! I i i i 506984 A7 ________ Β7 ___ 5. The invention description (19) was prepared. 3,4-dihydro-2-alkoxy-2H-pyran and 3,4-dihydro-2-phenoxy-2H- € ran are the corresponding zinc ethers of vinyl ether and acrolein in the catalyst amount It is prepared by reacting in the presence of a salt such as zinc chloride. Various 3,4-dihydro-2H-roanes having a substituent at the 2-position can be prepared by a similar reaction. The product formed by the reaction of 2 and 2 moles of acrolein with divinyl ether of polyalkylene glycol or polyalkylene glycol is also a protective agent. The latent thiols prepared from bis- (3,4-dihydropyranyl) ethers also have the potential to be used as chelating agents in the polymer composition of the present invention. In the reaction of each mole of divinyl ether with 1 mole of acrolein, the vinyl ether group of the obtained monomer allows the product to be incorporated into the vinyl chloride copolymer, followed by the addition of a thiol to cross the double bond of the pyran ring to Production of latent thiols (a stabilizer for the polymer as a whole). The reaction of 1 mole of acrolein with 1 mole of divinyl ether can also form a thiol / tetrahydropyran adduct-type monomeric latent thiol, in which the vinyl ether group of the obtained monomer allows the product to react with One or more different unsaturated vinyl compounds are copolymerized to form a polymerized latent thiol. The reaction product of acrolein and chloroethyl vinyl ether provides a substituted 3,4-dihydropyran which can be further derivatized. The reaction of adding a thiol to cross the double bond of the pyran ring can be performed in the presence of a zinc salt catalyst to produce the stabilizer composition of the present invention. In general, the step of adding a free thiol group that crosses the double bond of a polarized unsaturated compound is as follows: The thiol, acid catalyst, and any small amount of free radicals used to inhibit the free radical reaction in the stirring To the mixture formed by the antioxidant, a polarized unsaturated compound (pure or solution) was added dropwise under nitrogen, and the temperature was maintained at 10 at this time. -70 ° C, followed by heating the mixture or solution at 35 ° -70 ° c for 1 to 6 hours, and the conversion of the product was monitored by gas chromatography and iodine titration SH. Use alkaline washing This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -22-(Please read the precautions on the back before filling this page)

506984 A7 ---- B7 V. Description of the invention (20) To remove the acid catalyst, the obtained product is dried over magnesium sulfate and filtered. If necessary, the solvent is removed at <50 ° C to obtain a latent thiol. A solid phase catalyst can be used, which can then be filtered from the reaction mixture and regenerated in subsequent reactions. This method can omit the rinsing step. This step of regeneration is hereinafter referred to as step A. According to step A ', for example, fluorenylethanol is added to cross the double bond of N-vinylcaprolactam to produce N-2-hydroxyethylthioethylcaprolactam. In this step, ethyl decanoate (or ethyl hexanoate; or taUate ethyl acetate) is reacted with 3,4-dihydropyran to produce 2-S- (tetradecanoate Hydropyranyl) thioethyl (or 2-S- (tetrahydropyranyl) thioethyl hexanoate; or taUate 2-S- (tetrahydropyranyl) thioethyl). Bis (hydroxyethylthioethyl) cyclohexyl ether is prepared from fluorenyl ethanol and cyclohexyl divinyl ether. According to the same method, the corresponding decanoate, oleate and tallate form the corresponding cyclohexyl ether. Similarly, indene is converted to 2 fluorene-dihydroindenethioethanol by addition of fluorenylethanol. The general procedure for the condensation reaction of free thiols with unstable halogenated compounds is as follows: In a stirring mixture of a thiol and a halogenated compound, a methanol solution of sodium methoxide is added dropwise under nitrogen while maintaining The temperature is below 50 ° C. The reaction is arbitrarily carried out without adding an alkali source substance. The released hydrogen chloride is removed by a nitrogen scavenger, and it is neutralized by an external acid scavenger. Heating at 50 ° -70 ° C for 2 to 24 hours, and the conversion of the product was monitored by gas chromatography and iodine titration to monitor% 311. The product was then neutralized, washed with water, dried over magnesium sulfate, and filtered. If necessary, the solvent was removed at low pressure and <50 ° C to obtain a latent thiol. This step is hereinafter referred to as the paper size applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -23-(Please read the precautions on the back before filling this page) 部 部 部 fe »曰 慧 材 ioRwrr Shaugh A, i, f 鞑

_ · N ί ϋ i_i 1_1 one: eJ1 nn -ϋ ϋ nn ϋ I ϋ n I n I nnn II nnnn ϋ 1 n ϋ I n I— I %% ii% 506984 A7 ____B7____ V. Description of the invention ⑵) as a step B. The general procedure for the condensation reaction of free thiol with unstable hydroxy-containing compounds is as follows: .. Add the hydroxy-containing compound (pure quality) to the mixture formed by the thiol, acid catalyst and solvent while stirring. (Or a solution), at this time keep the temperature at &lt; 45 ° C, then heat the solution at 45 ° -7 5 ° C for 1 to 10 hours, and the conversion of the product is monitored by gas chromatography and iodine titration.% S Η . Optionally, an azeotropic solvent is selected and the reaction water is removed by an appropriate device at reflux temperature (typically 60.-120.0). The reaction is completed after the theoretical amount of water is collected. Washing with an alkali to remove the acid catalyst, The resulting product is dried over magnesium sulfate and filtered, and the solvent is removed at <5 5 ° C to obtain a latent thiol. This step is hereinafter referred to as step C. For example, 2-hydroxybenzyl alcohol and fluorenyl alcohol are based on The method of step C is condensed to produce 1- (2-hydroxyphenyl) -1S- (2-hydroxyethylthio) methane. The general steps of the condensation reaction of free thiol with glycidyl ether are as follows: Glycidyl ether (pure or solution) is added to the mixture formed by thiol and acid catalyst under nitrogen, and the temperature is maintained at 25 ° -60 ° C, and then the mixture or solution is at 50 ° -75 ° C. Heating for 1 to 6 hours, and the conversion of the product was monitored by gas chromatography and iodine titration to monitor% SH. The alkali catalyst was used to remove the acid catalyst, and the resulting product was dried over magnesium sulfate and filtered, if necessary, at low pressure and &lt; Remove the solvent at 55 ° C to obtain a latent thiol. For example, fluorenyl ethanol The reaction with glycidyl neodecanoate yields C9Hi9C (= 0) OCH2CH (OH) CH2SCH2CH2〇H. This step is hereinafter referred to as the paper standard applicable to China National Standard (CNS) A4 (210 X 297 mm). 24 -(Please read the precautions on the back before filling in this page) -I -------- Order --------- Lines-· -II n II &lt; 506984 A7 -----___ B7__ 5 2. Description of the invention (22) is step D. The general steps of the condensation reaction of free thiol and aldehyde are as follows: The aldehyde, thiol, acid catalyst and azeotropic solvent are added to the aldehyde under nitrogen while stirring. , And heated under reflux to remove the reaction water (usually 65 ° -1 20 ° C), the reaction is completed after the theoretical amount of water is collected. Optionally, under reflux, the thiol, aldehyde and ether are stirred BF3-diethyl ether solution was added dropwise to the solution. The conversion of the product was monitored by gas chromatography and iodine titration. The alkali catalyst was used to remove the acid catalyst. The resulting product was dried over magnesium sulfate and filtered. The solvent is removed at C to obtain a latent thiol. This step is hereinafter referred to as step E. The protected thiol of the present invention Examples include the compounds shown by the following chemical formulas, each of which corresponds to formula i: Formula 2. (Please read the precautions on the back before filling this page). · Order i

CIC CIC / ο

N ch3chsch2ch2oh a = l, m = l, n = 0, y2, z21; x is nitrogen, R6 and R7 together form &lt;! 12-(: 112-(: Za-(: (= 〇) -; 114 is hydrogen; &amp; 5 is methyl; and 1 ^ is hydroxyethyl. The paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -25- 506984 A7 B7 V. Description of the invention (23.0 ch3II I CH -cN-CH-S-CH2CH2OH I CH, m; X is nitrogen, R6 is ethynyl, R7 is methyl, R5 is methyl; R4 is hydrogen; and R1 is hydroxyethyl 4. sch2ch, oh 〇 m, y; χ is oxygen, R5 and R7 together form -CH2-CH2-CH2-CH2-; R4 is hydrogen, and R1 is hydroxyethyl. Η ο 2 Η c 2 Η- cs-〇II oa -I nfo IIm y

X H c Hua 2 H c 2 H c-Formation

0. Said 疋 and 4 R f 2 R R 棊 3 and ethyl R hydroxy, yes oxygen R1 and above (Please read the precautions on the back before filling this page)

This paper size applies to China National Standard (CNS) A4 (210 χ 297 mm) -26- 506984 A7 B7 V. Description of the invention (24 6.

a = l, m = 0, n = 0, y = l, z = l; x is oxygen, R5 and R7 together form -CH2-CH2-CH2-CH2-; R4 is chlorine, and R1 is 2-ethyl Oxytetrazolyl. (Please read the notes on the back before filling out this page); · Order -----

Line — · Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs have printed a = l, m = 0, n = 0, y to form -CH2-CH2-CH2-CHh; 8.1, z = l; x is oxygen, R5 and R together-R4 is hydrogen and R1 is 3-ethoxytetrahydropyridine 0

-OCH.CH.S— Π

This paper size applies the Chinese National Standard (CNS) A4 specification (210 χ 297 mm) -27-506984 A7 B7 Intellectual property staff of the Ministry of Economic Affairs 11 Consumption ^ 咋? £ 5. Description of invention (25) a = 1, m = 0, η: -CH2-CH2-CH: hydropyranyl is formed. 9. a = 1, m = ϋ, η forms -CH2-CH2-CH: hydropyranyl. 10 a.m R: 1, ζ = 1; X is oxygen, R3 and R7—from R4 and R5 are hydrogen, and R1 is 2-ethoxytetra η

-OCHnCH,, y = l, z = l; X is oxygen, R3 and R7—from R2, R4 and R3 are hydrogen, and R1 is 3-ethoxytetrasch? Ch7oh (please read the precautions on the back first) (Fill in this page)-〇CH, y, R5 is hydrogen, and V is hydroxyethyl 10b.

m and yz = 1; x is phenyl and r4 is methyl; x is phenyl and R: R. --ot nn an nn II— I nna · — n- nnnn ϋ i Bn n an an nn an flu nn I— I n This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) -28- 506984 A7 B7 V. Description of the invention (26) R4 and R5 are hydrogen and R1 is hydroxyethyl. 1 1.

—CH, SCH, CH, OH a = U, m = U, n = U, y hydrogen, and R1 is hydroxyethyl. 12. z = l; x is phenyl, R and R are (Please read the notes on the back before filling in this page)

OH

-CH2SCH2CH2OH a = 1, m = 0, n = 0, y = 1, z = l; X is phenyl, R4 and R5 are M, R is 0-hydroxyl, and R1 is hydroxyethyl. 13. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

: h, sch2coch, ch, sh1 丨 ... 〇 a = 0, m = U, η = ϋ, y = 1, z hydrogen, and R1 is fluorenylethoxycarbonylmethyl. Yes phenyl, R4 and R5 are-^-r0J · n an I ϋ nnn II nn ml I nn ϋ n I ϋ ϋ ϋ I nnn II nn «I-This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) -29-506984 A7 B7 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs on the consumption cooperation of employees V. Invention Description (27 14. CH, 〇

—OCH.CH

SCH2CH2OH a = 1, m = 0, η = 1, y = 1, z = 1; x is oxygen, R2, R4 and R5 are hydrogen, R3 is methyl, R7 is phenyl, and R1 is hydroxyethyl. 15. CH, — CH, plant \ 's 0 • ch' I ch3ch, ch7 a = 1 λ m = 〇, n = U, y two 1, z = formation of ethylene, R4 is hydrogen, and R5 is propyl Base 16 .; x is oxygen, R7 and R1 together (Please read the notes on the back before filling in this page) ·· —— CH, 〇

—OCH2CHCH2SCH2CH2OH OH a = 0, m = l, n = l, y = l, z two 1; x is oxygen, R2, R3, R6 one. t I in inn n- ϋ · ϋ I ϋ I ϋ Hi n J nn _ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -30- 506984 A7 B7 Employees ’Intellectual Property Bureau, Ministry of Economic Affairs Cooperative 钍 print 5. Description of the invention (28) and R4 is hydrogen, R5 is 2-propenyltolyl, and R1 is hydroxyethyl. 17.

CH3CH2CH2CH2OCH2CHCH2SCH2CH, OHI-OH a = 1, m = 0, n = 1, y 21, z = l; x is oxygen, R2, R3, R and R7 are hydrogen, R5 is butoxymethyl, and R1 is hydroxyl Ethyl. 18.sch2ch2oh /: H \ CH.CH, a = 1, m = 0, n = 0, y = 1, zdi1; x is phenyl, R4 is hydrogen, R5 is ethyl, and R7 is o-hydroxyl And R1 are hydroxyethyl. 19. OH _ 'SCH2CH2OH ch3 This paper size is applicable to the Chinese National Standard (CNS) A4 (210 x 297 mm) -31-(Please read the precautions on the back before filling this page). · One-mouth, ·· n I n 1 · 1 II ϋ nnnil ϋ— iln · ϋ I] ϋ ϋ ϋ n 506984 A7 B7 V. Description of the invention (29) m, η R5 is hydrogen, R2 is methyl 20. y = l, ζ = 1; χ is phenyl, R R7 is 0-hydroxyl, and R1 is hydroxyethyl. R4 and hochch, s CH— CH, CH,

SCH7CH7OH —CH ch2ch3 a di 1 'm = 0, n = 0, y = l, z di 2; x is phenyl, R4 is ammonia, R5 is ethyl, R7 is hydroxyl, and R1 is hydroxyethyl. 21. ch3o HO-

sch2ch2oh / CH \ ch7ch, a: l, m two 0, n = 0, y = l, z: l; x is ortho-methoxyphenyl, R4 is hydrogen, R5 is ethyl, R7 is P-hydroxyl, And Rl is hydroxyethyl. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -32-(Please read the precautions on the back before filling this page) * n ϋ ϋ nn ϋ n 1: 0_ i an nnn I nn I lilnnn-506984 A7 B7 V. Description of the invention (30) 22. ch2sch2ch2〇h CL ^ \ c ©

Cl

Cl

CH2SCH2CH2OH a = U, m = ϋ 'n = (J, y R5 is hydrogen, and R1 is hydroxyethyl. 23. z = 2; x is tetrachlorophenyl, R4 and

CH3CH2CHSCH2CH2OH (Please read the notes on the back before filling out this page) Member of the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumption Coordinator Wang printed «nnn ϋ ϋ nn a-0,» II nnnnn I ltin a. A: l, m = 0, n = 0, y21, z = 1; x is n- once-phenyl, R7 is 3L-phenylcarbonyl, R4 is hydrogen, R5 is -CKhCH; and R1 is hydroxyethyl. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -33-506984 A7 B7 Printed by the consumer cooperation of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (31 2 ^ · m, y 0 SCH2CH2OCC9Hl9 0

z = l; χ is oxygen, R5 and R7 form together-CH2-CH2-CH2-CH2-; R4 is hydrogen, and R1 is decyloxyethyl 25. HO- ◎ ch3o (Please read the notes on the back first (Fill in this page again)

-CH SS ~ CH2CH2OH a 1,2, m = 0, n = 0, y = l, z = l; x is via phenyl, R4 and R5 are hydrogen, R7 is SL-methoxy, and V is hydroxyl Ethyl. 26. C — c order --------- line! r— IIII-〇: sch2ch2oh This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) -34- 506984 A7 ---- B7 _____ 5. Description of the invention (32) OAlk 9 ° 6 ^ I Iο ρ sch2ch2oh sch2ch2oh HC = 0 I-〇I SCH2CH2OH. The compound used in the method of the present invention with a latent thiol is a free phenyl salicylate compound. The term "free phenylsalicylate" herein means that the phenylsalicylate is used independently in the stabilizer composition of the present invention, that is, it is physically used instead of being directly bonded to tin. Atomic ligands exist. The phenyl salicylate compounds suitable for the purpose of the present invention are as shown in the following formula 2: (Please read the notes on the back and fill in this purchase) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs H 0 0

(R20) x "B (II) wherein R2 () and R21 are each independently selected from hydrogen, alkyl, phenyl, alkoxy, phenoxy, alkylcarboxy, hydroxyl, halo, carboxy, benzamidine Group, glycidyl, glycidylamino, alkylamino, amido, hydroxypolyalkoxy, alkoxypolyalkoxy, or fluorenyl polyalkoxy; and X is an integer from 1 to 4, This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) -35-

-· 1 -I- n iMMmm n n ^ OJ «n n n ϋ n · 1 ϋ I I 506984 A7 B7 5. Description of the invention (33) and y are integers from 1 to 5. The preferred phenylsalicylate is in formula II where R2 {) is hydrogen and X is 4 and R21 is a hydrogen atom and y is 5 or R21 is an alkyl group having about 1 to 12 carbon atoms and y is 1 By. Examples of phenyl salicylate compounds are preferably phenyl salicylate, 2'-dodecylphenyl salicylate, 4'-methoxyphenyl salicylate, 4-methoxy salicylate Phenyl ester, 4, -chlorophenyl salicylate, 4-ethylamidophenyl salicylate, 1-hydroxy-2-phenyl naphthoate, 5-chlorophenyl salicylate, and salicylic acid 4-N-glycidylaminophenyl ester, although preferred structures are represented by phenylsalicylate and 2'-dodecylphenylsalicylate. The apostrophe (') indicates the R21 substituent, while the R2 ° substituent is not apostrophe. Those skilled in the art will appreciate that derivatives of phenylsalicylate, such as the corresponding benzamidine or pyridyl structures, can also be used, although from a relatively low thermal stability point of view At present, such derivatives are not more suitable. These phenyl salicylate can be produced according to standard methods disclosed in the prior art. Unless otherwise specified, in the above chemical formula and throughout the specification, the organic group referred to refers to a straight or branched chain group containing, for example, about 1 to 20 carbon atoms, and `` polyethylenyl '' means 2 or More heavy ΒΒΕΓ eg / -X-. Formed by the indicated group. As mentioned above, the stabilizer composition of the present invention contains a latent thiol as the sole thermal stabilizer, or a thermal stabilizer containing a metal substrate, a Lewis acid, and a thermal stabilizer containing an organic substrate. Agent, or a thermostabilizer with hyckotalcite as the substrate, mixed with a latent thiol. For the purpose of the present invention, gold is used. The thermal stabilizer used as the substrate is defined as the gold paper size applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -36-(Please read the note on the back first Please fill in this page again for the order) Order --------- Line 丨 · Investigator of the Ministry of Intelligent Materials 11 Xiao Cha iM 506984 A7 V. Description of the invention (34 belongs to salt stabilizer and organometallic stabilizer. Metal Salts are defined as containing oxides, hydroxides, sulfides, sulfates, chlorides, bromides, fluorides, iodides, phosphates, phenates, perchlorates, carboxylates, and carbonates. Metals Examples of salt stabilizers are phenol, aromatic carboxylic acids, fatty acids, epoxidized fatty acids, oxalic acid, carbonic acid, sulfuric acid, and barium, osmium, calcium, cadmium, zinc, lead, tin, magnesium, cobalt, nickel, titanium , Antimony and aluminum salts. Examples of suitable salts are calcium stearate, calcium 2-ethylhexanoate, calcium caprylate, calcium oleate, calcium ricinoleate, calcium myristate, calcium palmitate, calcium laurate, Barium laurate, barium stearate, zinc bis (nonylphenol), magnesium stearate, zinc stearate, zinc caprylate, 2-Zinc ethylhexanoate, zinc stearate, zinc laurate, zinc oxide, zinc chloride, zinc hydroxide, zinc sulfide, zinc sulfate, zinc bromide, cadmium laurate, cadmium octoate, cadmium stearate, Sodium stearate, and other Group I and II metal soaps. Other metal salts such as lead stearate, tin stearate, aluminum stearate, and hydrodirotalcite can also be used. Metal salt stabilizers The amount may be about 0.01 to about 10% by weight, preferably 0.1 to 5% by weight of the halogen-containing resin. Traditional organometallic stabilizers include organotin carboxylate and thiolate. Such materials include butyltin tris Alkylthiol) salts, dibutyltin dilaurate, dibutyltin di (dodecanethiol) salt, tris (dibutyltin) diol dianhydride, dialkyltin salts of carboxythiols, for example Hechenbleikner et al. In the United States Disclosed in Patent 3,078,290. Also included are vinyl chloride resin stabilizers disclosed in US Patent No. 2,985,6 1 7 to Salyer. Examples of preferred organotin thiolates include mono- or di-Ci-Cu alkylthiothioacetates Alkyltin thiolates, such as tris (2-ethylhexylthioacetic acid) -methyl Tin, bis (2-ethylhexylthioacetic acid) dimethyltin, tris (2-ethylhexylthioacetic acid) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -37 (Please read the precautions on the back before filling this page) # Order --------- line 丨 一 506984 A7 _ B7 V. Description of the invention (35) (Please read the precautions on the back before filling this page ) Monobutyltin, di (2-ethylhexylthioacetate) dibutyltin, tris (2-ethylhexylthioacetate) -octyltin, and di (2-ethylhexylthioacetate) dioctyltin , And mono- or dialkyltin thiolates of oxalic acid carboxylates, such as tris (ethyl oleate) monomethyltin, di (diethyl oleate) dimethyltin, tris (nonyl Ethyl acetate) monobutyltin, and di (tin ethyl azelate) dibutyltin. Examples of preferred organotin carboxylates include mono- or di-C〃Cl2 alkyltin carboxylates, such as tris (maleic acid dodecyl) monobutyltin, bis (butylene maleate) (Esters) dibutyltin, diethyltin azelate, diethyltin dilaurate, dimethyltin dibenzoate, dimethyltin di (butyl maleate) dimethyltin, and bis (cis Butylene glycol butylene diacrylate) dimethyltin, and its oligomers or polymer salts. Particularly suitable for the purpose of the present invention are mixtures of mono · or di-alkyltin thiolates. The monoorganotin compounds and diorganotin compounds of the composition of the present invention can be prepared by techniques known in the art, such as Or the dialkyltin chloride is reacted with a pinane carboxylate or an alkylthioacetate in the presence of a base capable of removing hydrogen chloride. Examples of organic chlorides suitable for preparing the stabilizer of the present invention include methyltin trichloride, dimethyltin dichloride, butyltin trichloride, dibutyltin dichloride, ethylhexyltin trichloride, and Dioctyltin chloride. For other examples, see U.S. Patents 3,565,930, 3,869,487, 3,979,359, 4,118,371, and 4,183,846, the contents of which are incorporated herein by reference in their entirety. Monosulfides and / or polysulfides of arsenyl carboxylates and / or alkylthiothiolates of organotin thiolates are also suitable for use in the composition of the present invention as a metal-based thermal stabilizer to Improves the properties of halogen-containing polymers against the deterioration caused by heating to 3 50 ° F (177 ° C) during processing. The sulfide is applied to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -38-506984 A7 B7 via this paper size V. Description of the invention (36) (Please read the precautions on the back before filling this page) Prepared by heating the stoichiometric pinane ester or alkylthiocarboxylate with organotin chloride in water and ammonium hydroxide to about 30 ° C, slowly adding alkali metal mono- or polysulfides, and then The reaction mixture was heated to about 45 ° C and the product was isolated from the mixture. Alternatively, sulfides can be prepared by mixing mono- or di-alkyltin sulfides with organotin thiolates and other stabilizers, as is well known in the art. Economics Zou Zhicai 4¾ members X. Consumption combination fi. Printed alkyltin sulfonate carboxylate or sulfonate carboxylate is characterized by one or more alkyl tin halides, one or more organotin An equilibrium mixture of thiolates and one or more alkyl tin mono- or polysulfides or their oligomers. It must be understood that the structure of the sulfide produced by the above method is very complicated. I believe that the reaction produces an equilibrium mixture of several different but related products. Those familiar with chemistry know that the equilibrium mixture essentially contains the starting materials of the reaction and the products of any reaction between them. The chemical and patent literature contains many examples demonstrating that many different classes of organotin compounds can react with one another under specific conditions to produce products containing one or more tin atoms, at least a part of which is a tin atomic bond To a combination of different groups before mixing with it. Therefore, I believe that sulfides contain bis · [mono (organotin) -bis (sulfanyl carboxylate)] monosulfides and polysulfides, bis [(diorganotin) -mono (sulfanyl carboxylate)] Monosulfide and polysulfide, and products formed during the equilibrium reaction between the monosulfide and polysulfide, include monoalkyltin tri (sulfanyl carboxylate), dialkyltin di (sulfur carboxylic acid) Alkyl esters), mono- and di-organotin monosulfides and polysulfides, and their oligomers, as well as the reaction initiators themselves. Similarly, I believe that the sulfides of alkyl carboxylic acid alkyl esters include bis- [mono (organic tin) -bis (alkyl carboxylic acid alkyl)] monosulfides and polysulfides, and bis [(diorganic 39 paper size applies China National Standard (CNS) A4 specification (210 X 297 mm) 506984 A7 B7__ V. Description of the invention (37) Tin) -mono (alkyl carboxylic acid alkyl ester)] monosulfide and polysulfide, and the monosulfide Products formed during equilibrium reactions with polysulfides, including monoalkyltin tris (alkylene carboxylates), dialkyltin bis (alkylene carboxylates), mono- and di-organotin monosulfides And polysulfides, and their oligomers. Polysulfides include a mixture of compounds having 2 to 10 sulfur atoms bonded together. Mixtures of monosulfides and polysulfides having 2 to 10 sulfur atoms are preferred. The organometallic stabilizer is about 0.01 to about 10% by weight of the halogen-containing resin, preferably 0.1 to 5% by weight. Other stabilizers that can be used with latent thiols include Lewis acid. Examples of Lewis acids are boron trifluoride, aluminum chloride, zinc chloride and methyltin trichloride. Therefore, the metal salts that can be used in the present invention overlap somewhat with the Lewis acid. The synergistic amount of the Lewis acid used for the purpose of the present invention is about 0.005 to 0.5% by weight, preferably 0.01 to about 0.1% by weight, of the halogen-containing resin. Lewis acid and metal stabilizers can be used. The stabilizer composition of the present invention may also include conventional non-metallic stabilizers to help improve the properties of the halogen-containing resin. Therefore, it may contain about 0.01-10%, preferably 0.1-5%, of the halogen-containing resin, and sulfur-containing compounds such as dilauryl thiodipropionate, distearyl 3,3'-thiodipropionate , 3,3, Dicyclohexylthiodipropionate, 3,3'-thiodipropionate dioleate, 3,3'-thiodipropionate dibenzyl ester, 3,3'-sulfur Didecyl dipropionate, 3,3'-thiodipropionate dibenzyl ester, 3,3, diethyl thiodipropionate, lauryl 3-methylthiopropionate, 3-butylsulfide Lauryl propanoic acid, lauryl 3-propanoic acid, and phenyl ester of 3-octylthiopropionic acid. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) -40- (Please read the precautions on the back before filling this page) Order --------- line 丨 ·- ----.——.----- 1 -------- Qiί 'tt 506984 A7 -------- _B7 _ V. Description of the invention (38) In addition to the stabilizer composition of the present invention In addition, traditional additives such as plasticizers (used for flexible PVC), foaming agents, dyes, UV co-absorbers, antioxidants, and thickeners can also be incorporated. Agents, biocides, impact modifiers, processing aids, stabilizers, toners, etc. The halogen-containing polymer composition stabilized by the stabilizer composition of the present invention is generally limited to a clear blend. These blends therefore contain little or no pigments or extenders that will make them opaque. Since I do not want to be limited by any particular reasoning, I believe that the sufficient energy (hv) is provided in the clear blend, so that the corresponding functional activity can be obtained by the photo-induced Fnes rearrangement of the phenylsalicylate compound. Benzophenone structure, which can absorb a high amount of ultraviolet radiation throughout the clear polymer composition. When it comes to dyeing or tincture-filling (ie, opaque) blends, we believe that most of the phenylsalicylate compounds' photoinduced Fnes rearrangement to their functionally active form will be blocked. The amount of antioxidant is 0.01-10% by weight of the resin, preferably 0.1-5% by weight. Phenol-based antioxidants are particularly suitable, examples of which are 2,6-di-third-butyl-p-cresol, butylated hydroxyanisole, propyl gallic acid '4, 4, thiobis (6- Tertiary butyl-m-cresol), 4,4'-cyclohexylene diphenol, 2,5-di-tertiary pentyl hydroquinone, 4,4'-butylene bis (6-third butyl- M-cresol), hydroquinone monobenzyl ether, 2,2, methylene bis (4-methyl-third butylphenol), 2,6-butyl-4-decylphenol, 2-third Butyl-4-dodecyloxyphenol, 2-third butyl-4-octadecyloxyphenol, 4,4'-methylenebis (2,6-third butylphenol), p- Aminophenol, N-lauryloxy-p-aminophenol, 4,4'-thio double paper size applicable to China National Standard (CNS) A4 (210 X 297 mm) -41-(Please read the back first (Please note this page before filling out this page); -------- Order --------- Line 1 ------------ Ί -------- ----- 506984 A7 B7 V. Explanation of the invention (39) (3-methyl-6-third butylphenol), bis [o- (i, i, 3,3-tetramethylbutyl) phenol ] Sulfide, 4-fluorenyl-β-dihydroxybenzoic acid, p-third butylphenol methyl ester in A-stage Resin, 4-dodecyloxy-2-hydroxybenzophenone, 3-hydroxy-4- (phenylcarbonyl) phenyl palmitate, 3-hydroxy-4- (phenylcarbonyl) phenoxyacetic acid n-dodecyl Alkyl esters, and third butylphenol. It is also beneficial to use from 0.01 to 30% of an epoxy stabilizer compound in the polymer composition. Examples of this epoxy compound include epoxidized soybean oil, epoxidized lard, epoxidized olive oil, epoxidized linseed oil, epoxidized castor oil, epoxidized peanut oil, epoxidized corn oil, epoxidized Oxidized tung oil, epoxidized cottonseed oil, epichlorohydrin / bisphenol A resin, phenoxypropylene oxide, butoxypropylene oxide, epoxidized neopentenyl oleate, epoxy stearate shrink Glyceryl esters, epoxidized alpha-olefins, epoxidized soyate glycidyl esters, dicyclopentadiene dioxide, epoxidized butyl phenylacetate, styrene oxide, dipentene dioxide , Glycidol, ethylene cyclohexene dioxide, resorcinol glycidyl ether, hydrogen ester glycidyl ether, 1,5-dihydroxynaphthalene glycidyl ether, epoxidized linseed oil fatty acid, allyl glycidol Ether, butyl glycidyl ether, cyclohexane oxide, 4- (2,3-glycidoxy) ethenylbenzene, fluorenyl oxide epoxide, 2-ethyl-3 -propyl glycidyl Amidine, glycamine, glycidyl glycidyl ether, pentaerythritol and sorbitol, 3,4-epoxy-cyclohexane-1,1-dimethanol bis-9,10-epoxy stearate. Likewise, an organic phosphite which is 0.01 to 10% (preferably 0.1 to 5%) of the halogen-containing resin may be used. Organic phosphites contain one or more (up to 3) aryl, alkyl, aralkyl, and alkaryl groups (including any combination of forms). "Trialkylaryl-42- (Please read the precautions on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 506984 A7 __—__ B7___ 5. Description of the invention ( "40)" means an alkyl phosphite, aryl ester, alkaryl ester, and aralkyl ester containing any combination of aryl, alkyl, aralkyl, and alkaryl groups. Examples are triphenyl phosphite, tri (tolyl) phosphite, tri (xylyl) phosphite, tributyl phosphite, trioctyl phosphite, tris (dodecyl) phosphite , Octyl di (phenyl) phosphite, bis (octyl) (phenyl) phosphite, tris (octylphenyl) phosphite, tris (nonylphenyl) phosphite, tris Benzyl ester, (butyl) bis (tolyl) phosphite, (octyl) bis (octylphenyl) phosphite, tris (2-ethyl · · hexyl) phosphite, tris (toluene) acid Ester), tris (2-cyclohexylphenyl) phosphite, tris (α-naphthyl) phosphite, tris (phenylphenyl) phosphite, and tris (2-phenethyl) phosphite ester. Similarly, the vinyl chloride resin may use 0.01-10% by weight of a polyalcohol stabilizer. Therefore, glycerol, sorbitol, pentaerythritol, and mannitol and polyethers such as diethylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, and the like may be contained. Qi i also can use 0.1-10% by weight of nitrogen-containing stabilizers such as dicyandiamide, melamine, urea, formoguanamide, dimethyl caprolactam, guanidine , Thioureas, 2-phenylindoles, aminocrotonates, N-alkyl and N-phenyl substituted maleimides (where alkyl groups have 1 to 4 carbon atoms) , Uracil and so on. Particularly interesting compounds are 1,3-dialkyl-6-aminouracil derivatives (disclosed in German Patent No. 19,741,778 of Ciba Specialty Chemicals Holding Inc) and pyrrodiazine dione (disclosed in Ciba-Geigy). Australian patent case AU-A-48232 / 96) and the like, and its amount is 0.1-10% by weight. A particularly interesting compound is the pyrrolodiazine dione represented by the following formula: a -43- (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297) (Mm) 506984 The Ministry of Economic Affairs temporarily 犲 肖 members of the two Xiao Fei &quot; Cha: A7 ____B7 V. Description of invention ⑷)

Where R①, R②, R③, and R④ are hydrogen or C ^ C4 alkyl, respectively. Examples of the compounds used in the present invention include the 1H-pyrrolo [2,3-d] chelate-2,4 listed in the above-mentioned Australian patent case as compounds Nos. 10, 11, 11, 123, 129, and 131 (3H, 7H) -diketone compounds having the following substituents: No. 103: 1,3,6-trimethyl; No. 111: 1,3,6,7-tetramethyl; No. 123: None; No. 129: 1,3-diethyl, 6-methyl; No. 131: 1,3-dibutyl, 6-methyl; This compound is available from S. Senda and K. Hirota , Chem. Pharm. Bull., ^ 1 (7), 1 459-1 467 (1 974), or by the following method: the corresponding amine uracil and Mortal excess of ethyl chloride The aldehyde and ammonium acetate are reacted in water at 65 ° C until a precipitate is formed, or they are reacted with a molar excess of ethoxylated acetone and ammonium acetate in water under reflux for 12 hours. German patent case 19,741,778 and Australian patent case AU-A-48232 / 96 are incorporated herein by reference. Even conventional lubricants that can include vinyl chloride resins, such as low molecular weight polyethylene (ie, polyethylene wax), fatty acid amines such as lauramine and stearylamine, bisamides such as decylbisamine, and fats Ester such as butyl stearate This paper is sized for Chinese National Standard (CNS) A4 (210 X 297 mm) -44-(Please read the precautions on the back before filling this page) -1 0 ί i ϋ nnnn 1 t I ΜΙ · mm I MM Maw I n. 506984 A7 __ B7 V. Description of the invention (42) esters, glyceryl stearate, linseed oil, palm oil, decyl oleate, corn oil, cotton oil, Good oil such as hydrogenated cotton. The stabilizer composition of the present invention can be prepared by pre-blending the components by any convenient method to obtain a homogeneous mixture, for example, by shaking or stirring in a container. Similarly, the stabilizer composition and the polymer may be mixed, for example, in a suitable honing machine or mixer, or by other methods known to uniformly distribute the stabilizer throughout the polymer. The stabilizer composition of the present invention is incorporated into a halogen-containing organic polymer. The stabilizer composition of the present invention is used in an amount sufficient for the halogen-containing organic polymer to obtain a desired anti-heat deterioration effect. Those skilled in the art can immediately understand that the correct amount of stabilizer composition will depend on several factors, including (but not limited to) the specific halogen-containing organic polymer used, the temperature to which the polymer will be subjected, And the possibility of other stable compounds. Generally, the more severe the halogen-containing organic polymer is, and the longer it takes to combat the deterioration, the higher the amount of stabilizer composition required. Generally, amounts as low as about 0.4% by weight based on the weight of the halogen-containing organic polymer are still effective. However, the upper limit of the amount of the stabilizer composition used is not strictly limited, and an amount exceeding about 4% by weight of the halogen-containing organic polymer will not result in a relatively higher effect due to the increase in the amount of the stabilizer. The examples further detail the preparation of the listed latent thiols, the preparation of the stabilizer composition of the present invention, and the advantages of the stabilizer composition in a clear halogen-containing polymer composition. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) -45- (Please read the precautions on the back before filling this page) · ------- 丨 Order ----- ---- line 丨 ---------- T -------------- 506984 A7 _____ B7 V. Description of the invention (43) Unless otherwise specified, stabilizer components And other auxiliary ingredients are expressed in parts by weight ("phr") per 100 parts of the halogen-containing resin. Example 1 Preparation of Latent Thiols Tal acid 2-S- (tetrahydropyranyl) thioethyl ester was prepared by the following method: at 25 -3 5 ° (:, 72.45 2 (2.05 (Equivalent) 3,4-dihydro (2pyran) is added dropwise to 760.00 g (2.00 equivalents) of 2-methyl ethyl tallate (contained by indirect iodine titration) containing methanesulfonic acid (70% active) 8.7% SH), for 45 minutes, and heated at 35-40 ° C for 2 hours. Cool the solution, add 3 g of Nonte carbon black, and vacuum filter the product to obtain 932 g of a yellow liquid. The product is 0.1 00 N iodine in isopropyl Alcohol solution titration showed that the SH content was less than 0.4%. The NMR (CDCh, δ) spectrum was: 2.3 (2H, t, -C (= 〇) -CH_2-CH2-), 2 · 8 (2H, m, -S -CH2-CH2-), 4.3 (2H, m, -CC (= 0) -0-CH2), 4.9 (1H, m, -〇-CH (-S-CH2) -CH2-CH2-). GC (1% ether solution) showed a main peak at a lag time of 26.3 minutes (50-300 ° C; 10 ° C / min; split syringe / FID). Example 2-5 Rigid and clear Preparation of PVC composition (Examples 2 and 3 are comparative examples) The following ingredients are blended according to the specified amount to make 4 kinds of clear polyvinyl chloride The composition of which the first two are stabilized with a latent thiol alone, and the latter two are prepared according to the present invention with a latent thiol and salicylic acid benzene paper in accordance with Chinese National Standard (CNS) A4 specifications 210 χ 297 mm) -46-(Please read the notes on the back before filling out this page) 1 11111--Order ---- I--III · 506984 A7 ___ B7 V. Description of the invention (44) The ester compound makes Stability. Ingredients Pi ir Example 2 Example 3 Example 4 ----- Example 5 PVC resin (Occidental 190) 100.0 100 100 100 Impact modifier (Kaneka B-22) 6.0 6.0 6.0 ------- 6.0 Processing Additive (Rohm &amp; Haas Acryloid K-120N) 1.5 1.5 1.5 1.5 Ester wax lubricant (Henkel Loxiol G-16) 1.0 1.0 1.0 1.0 Ester lubricant (Henkel Loxiol G-70) 0.7 0.7 0.7 0.7 Oxidizing Polyethylene lubricant (Allied AC-629A) 0.2 0.2 0.2 0.2 Epoxidized soybean oil stabilizer 1.0 1.0 1.0 1.0 Organotin thiolate 1 2.5 2.5 2.5 —............. 2.5 Latent thiol (Example 1) 0.5 0.5 0.5 0.5 Phenyl salicylate (Aldnch) ----0.25 0.25 Note (Please read the note on the back first (Please fill in this page again for the matters needing attention) Order——Inf pi Note 1: The organotin thiolate stabilizer is composed of 80 wt% dimethyltin bis (_ y oxalate 2-ethylhexyl) and 20 wt% A mixture of monomethyltin tris (2-ethylhexyl maleate). Each of the obtained polymer compositions was then made into plaques and exposed to ultraviolet (UV) and moisture and equipped with a QUV-A-351 lamp— — — — — — — — — — — — — — — — — — — — — — — — — — —- —---This Paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -47-506984 A7 B7 V. Description of the invention (45) The Q-Panel QUV accelerated weathering test machine of Pau test its stability to light and climate Sex. Each plaque was exposed to a concentration cycle of 10 hours of ultraviolet light and 2 hours of humidity at 50 ° C, and this step was repeated until each plaque had been exposed for 960 hours. Each sample was evaluated every 160 hours and the color was read using a Hunter colorimeter. The AE (total color change) readings for each composition obtained using the initial sample (hour 0) as the color reference are shown in the table below. ΔΕ hours 160 320 480 640 800 960 Example 2 18.95 17.39 24.01 25.89 28.06 30.13 Treasure example 3 18.50 19.07 28.86 23.4 9 24.89 31.03 Example 4 9.56 9.11 14.80 14.62 18.62 20.34 Example 5 10.52 11.00 15.25 17.45 20.15 19.02 (Please read the notes on the back first Please fill in this page again) The results obtained from the stupid f I discussion i L · above prove that: 1) the latent thiol system used alone is a poor weathering stabilizer; and 2) the weathering stability of the latent thiol system is related to The phenylsalicylate compound is significantly enhanced by mixing it in a clear polyvinyl chloride composition. Example 6-7 Preparation of a flexible and clear PVC composition (Example 6 is a comparative example) The following ingredients were blended according to the specified amount and tested for weather resistance according to the procedures disclosed in Examples 2-5, but using UV / 4-hour condensing cycle weekly order --------- line! The size of this paper is in the form of formazan brown (CNS) A4 U10 X 297 mm). 48-506984 A7 —— B7 V. Description of the invention (46) The period lasted 1 600 hours. Chou Qi Zou Shenhui inspector 11 Xiao F Ketutu ^ Preparation of Phr Example 6 Example 7 PVC resin (Geon 30) 100.0 100.0 Diisodecyl phthalate plasticizer 40.0 40.0 Epoxidized soybean oil stabilizer 5.0 5.0 Stearic acid lubricant 0.2 0.2 Oxidized polyethylene lubricant (Allied AC-629 A) 0.2 0.2 Latent mercaptan (Example 1) 2.0 2.0 Zinc octoate stabilizer 0.1 0.1 Phenyl salicylate ___ 0.1 ΔE hours 160 320 480 640 800 960 1120 1280 1440 1600 Example 6 9.7 0.7 2.4 12.3 14.5 18.2 21.5 19.0 22.7 22.2 Example 7 8.1 0.6 1.3 5.6 9.9 10.5 9.0 12.7 14.0 11.7 The results obtained above prove that: 1) the latent thiol system used alone is not good Weathering stabilizer; and 2) the weathering stability of the latent thiol system is mixed with the phenyl salicylate compound for clear polyvinyl chloride composition (please read the precautions on the back before filling this page) « · (1 1 ϋ n flu nn · nn I emmmmm I— MmmmM n 1 line — 4 ------ (—— I ------------ This paper size applies to Chinese national standards ( CNS) A4 size (210 X 297 mm) -49-506984

5. The invention description (47) is significantly enhanced. Example 8 Preparation of β c composition 11 plates 8 and 9 are for comparison. Η The following ingredients are blended according to the specified amount to make 2 kinds of dyed polyvinyl chloride composition, the first composition is separately Stabilization with latent thiol The second composition is stabilization with latent thiol and phenylsalicylate compound. (Please read the precautions on the back before filling this page) · n 1 / 1-1 in 1: OJ · -ϋ I nn 1 · nn I line 丨 wheel ------ 一 --- ^ --- ----------- Ingredient Phr Example 8 Example 9 PVC resin (Geon 30) 100 100 Dioctyl phthalate plasticizer 55.0 55.0 Calcium carbonate fluorene filler (OMYA UFT) 10.0 10.0 Dioxin pigment (Du Pont Ti-Pure 5.0 5.0 R-960) Epoxidized soybean oil stabilizer 3.0 3.0 Stearic acid lubricant 0.2 0.2 Oxidized polyethylene lubricant (Allied 0.2 0.2 AC-629A) Latent mercaptan (Example 1 ) 0.15 0.15 phenyl salicylate (Aldnch) —— 0.1 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -50-506984 A7 B7 V. Description of the invention (48) According to Example 6- The procedure described in 7 tests the QUV weather resistance of each of the resulting polymer compositions. The ΔE (total color change) readings for each composition obtained using the initial sample (hour 0) as the color reference are shown in the table below. ΔΕh 160 320 480 640 800 960 1120 1280 1440 1600 Example 8 0.4 0.8 2.1 0.9 1.5 1.5 1.0 1.7 2.4 3.0 Example 9 0.5 0.4 1.3 0.8 0.6 1.7 1.3 1.3 1.4 3.6 The above results prove that: 1) the latent sulfur used alone Alcohol systems are poor weathering stabilizers; and 2) Latent thiol systems mixed with phenylsalicylate compounds for dyeing polyvinyl chloride compositions do not receive the benefits of weathering stability because phenylsalicylate compounds are This is not functionally active. By the known conventional technique of forming polymers into molded articles, the stabilized polymer composition of the present invention can be made into, for example, pipes, films, exterior wall panels, window profiles, window frames, wave-shaped roofing materials, and door strips. Objects. Although a few specific systems of the invention have been disclosed in detail, changes and modifications to the system can be made without departing from the spirit and scope of the invention as disclosed herein and in the scope of the patent application. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) -51-(Please read the precautions on the back before filling this page) Order ------ Line!

Claims (1)

506984 VI. Annex 1 (A) of the scope of patent application: Π Patent Application No. 88.1 1 7624 !, &gt; t!} / Amendment of the scope of patent application in Chinese Amendment in the Republic of China in August 1990 1. A stable content The halogen polymer composition is a composition that resists the effects of heat, light and weather degradation, and includes: A) 50 wt% to 98.8 wt% (based on the total weight of A) and B) of a latent thiol And it can be degraded when the composition is processed at high temperature to release free thiol. The latent thiol is expressed by the following formula: (Please read the precautions on the back before filling this page) R7) X R4I C r21ivihjj SR Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs where a is 0 or 1, m and η are 0 or 1; y = 1 to 4; when y = 1, z is 1 to 4; and when y is greater than 1, z is 1; R1 is hydroxyalkyl, dihydroxyalkyl, hydroxy (polyalkoxy) alkyl, alkoxyalkyl, hydroxyalkoxyalkyl, alkoxy (hydroxyalkane) having 1 to 22 carbon atoms Group), alkoxy (alkoxyalkyl), alkoxy (polyalkoxy) alkyl, carboxyalkyl, fluorenyl alkyl, fluorenyl (hydroxyalkyl), fluorenyl alkoxy Base, alkoxy (polyalkoxy) alkyl, benzyl oxy (polyalkoxy) The paper size applies to the Chinese National Standard (CNS) A4 standard (210X297 mm) ~-1-506984 A8 B8 C8 D8 6. Scope of patent application (please read the notes on the back before filling this page) Printed alkyl groups, alkylidene groups (alkoxyalkyl groups), alkoxycarbonylalkyl groups, Alkoxycarbonylalkyl, hydroxyalkoxycarbonylalkyl, hydroxy (polyalkoxy) carbonylalkyl, alkoxy (polyalkoxy) carbonylalkyl, fluorenyl, fluorenyl, fluorenyl Carboalkyl, alkanoyloxyalkylene, alkoxycarbonyl (amido) alkyl, alkoxycarbonyl (polyalkoxy) carbonylalkyl, tetrahydropyranyloxyalkyl, tetrahydropyranyloxy (Polyalkoxy) carbonylalkyl, hydroxyaryl, olearyl or aryl; R2, R3, R4, R5, R6, and R7 are hydrogen, hydroxy, fluorenyl, fluorenyl, and have 1 to 22 Alkyl, alkylene, aryl, haloaryl, alkaryl, aralkyl, hydroxyalkyl, amidino, hydroxyaryl, alkoxyaryl, alkoxyhydroxyaryl, hydroxy alkyl , Fluorenyl, fluorenyl, fluorenyloxycarbonyl, hydroxyaryl, arylcarbonyl, fluorenyl, carboxyalkyl, carboxyaryl, or fluorenyl; X is aryl, haloaryl ' Alkylaryl, hydroxyaryl, dihydroxyaryl, aralkylaryl, alkoxyaryl, arylcycloalkyl, or heteroatom, or one of R3 and R5 when a is 1 and m is 0 Combined with R7 and X to form a heterocyclic group containing heteroatom X (X is selected from oxygen and sulfur), or when m is 1, R6 and R7 together form a heterocyclic group containing X as the connection point ( X is a nitrogen atom); but its prerequisite is that when X is aralkylaryl, R6 and R7 are hydroxyl, a is 1 and m is 1, then z is 1 or 2, and another prerequisite is when R6-hydroxyl Or fluorenyl, z is 1; and B) 1.2 to 50 wt% (based on the total weight of A) and B) of free phenyl salicylate. 2. The composition according to item 1 of the scope of patent application, wherein the composition is incorporated into the halogenated polymer composition of Chenghuang in a stable and effective amount. 3. If the composition of the scope of the application for the first item of the patent, there is additionally a heat stabilizer selected from the group consisting of metal as the substrate, Lewis acid, and organic materials as the substrate. The Chinese paper standard (CNS) A4 specification (210X297 mm)-2-506984 A8 B8 C8 _ D8 VI. Patent application scope Thermal stabilizers and thermal stabilizers with hydrotalcite as the substrate. (Please read the notes on the back before filling this page) 4 · If the composition of the scope of patent application item 3, the thermal stabilizer contains at least one metal-based thermal stabilizer, and it is selected from antimony , Barium, magnesium, calcium, tin or zinc as the substrate heat stabilizer. 5. The composition as claimed in item 4 of the patent application, wherein the metal-based heat stabilizer is zinc soap. 6. The composition according to item 3 of the patent application range, wherein the other heat stabilizers include at least one metal-based heat stabilizer, and the heat stabilizer is selected from organic tin compounds. 7. The composition according to item 6 of the application, wherein the organotin compound is a mono- or polysulfide selected from organotin thiolates, organotin thiolates, and organotin carboxylates. 8. The composition as claimed in claim 7 wherein the thiolate group is fluorenyl alkyl acetate. 9. The composition according to item 7 of the patent application, wherein the thiolate group is a pinane carboxylate. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. A clear halogen-containing polymer composition that has been stabilized to resist the effects of heat, light, and weather. This composition can make substantially transparent objects. The composition comprises a monohalogenated polymer, free phenylsalicylate, and a degradation product of a protected thiol present when the composition is processed at high temperature, the degradation product comprising free thiol; the protected The mercaptan system is as follows: This paper size is applicable to China National Standards (CNS> A4 size (210X297mm) -3-506984 A8 B8 C8 D8 々, patent scope R4 Tr2] -R1 (Please read the back Please fill in this page again for attention) 7 II (R) Α-Χ -CrCS— · (R6) m IR 'Lr3J0 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs where a is 0 or 1, and m and n are 0 or 1 y = 1 to 4; when y = 1, z is 1 to 4; and when y is greater than 1, z is 1; R1 is a hydroxyalkyl group, a dihydroxyalkyl group, a hydroxyl group having 1 to 22 carbon atoms (Polyalkoxy) alkyl, alkoxyalkyl, hydroxyalkyloxyalkyl, alkoxy (hydroxyalkyl), alkoxy ( Oxyalkyl), alkoxy (polyalkoxy) alkyl, carboxyalkyl, fluorenyl alkyl, fluorenyl (hydroxyalkyl), fluorenyl alkoxyalkyl, fluorenyl (polyalkoxy) ) Alkyl, benzamyloxy (polyalkoxy) alkyl, alkylidene bis (phosphonoalkyl), alkoxycarbonylalkyl, alkoxycarbonylalkyl, hydroxyalkoxycarbonylalkyl, hydroxyl (Polyalkoxy) carbonylalkyl, alkoxy (polyalkoxy) carbonylalkyl, fluorenyl, fluorenyl, fluorenyl, alkoxycarbonyl, alkoxycarbonyl, alkyl, alkoxycarbonyl (Fluorenylamino) alkyl, alkylcarbonyloxy (polyalkoxy) carbonylalkyl, tetrahydropyranyloxyalkyl, tetrahydropyranyloxy (polyalkoxy) carbonylalkyl, hydroxyaryl, Fluorenylaryl or carboxyaryl; R2, R3, R4, R5, R6, and R7 are hydrogen, hydroxy, fluorenyl, fluorenyl, alkyl having 1 to 22 carbon atoms, alkylene, aryl, halogen Aryl, alkaryl, aralkyl, hydroxyalkyl, fluorenyl, hydroxyaryl, alkoxyaryl, alkoxyhydroxyaryl, hydroxyalkyl, fluorenyl, sulfanyl, fluorenyl Carboxyalkylene, hydroxyaryl, arylcarbonyl, amaryl, carboxyalkyl Applicable to China National Standards (CNS) A4 (210X297 mm) ~ ΓΤΙ 506984 A8 B8 C8 ____P8 _ 6. Scope of patent application, carboxyaryl, or fluorenyl; X is aryl, haloaryl, alkylaryl , Via aryl, dihydroxyaryl, aralkylaryl, alkoxyaryl, arylcycloalkyl, or heteroatom, or when a is 1 and m is 0, one of R3 and R5 is the same as R7 and X joins together to form a heterocyclic group containing heteroatom X (X is selected from oxygen and sulfur) 'or when m is 1, R6 and R7 together form a heterocyclic group containing X as the point of attachment (X is nitrogen Atom); but its prerequisite is that when X is aralkylaryl, R6 and R7 are hydroxyl, a is 1 and m is 1, then z is 1 or 2, and another prerequisite is when hydroxyl or fluorenyl, z is 1. ! 1. According to the composition of the scope of application for patent No. 10, there are additionally selected from the group consisting of a metal-based thermal stabilizer, Lewis acid, an organic-based thermal stabilizer, and hydrotalcite ( hydrotalcite) is the thermal stabilizer of the substrate. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 橾 Home I Country One Country One Time I Use I Appropriate π 29